Hydrogenation of carbon monoxide with promoted iron catalyst



H. G. M GRATH HYDROGENATION OF CARBON MONOXIDE May 27, 1952 WITH PROMOTED IRON CATALYST Filed Feb. 1, 1947 INVENTORS flan firs: are awarx/ Patented May 27, 1952 HYDROGENATION OF CARBON MONOXIDE WITH PROMOTED IRON CATALYST Henry G. McGrath. Elizabeth, N. J., assignor to The M. W. Kellogg Company, Jersey City, N. J., a corporation of Delaware Application February 1, 1947, Serial No. 725,835

This invention relates to the synthesis of organic compounds. In one aspect this invention relates to the hydrogenation of an oxide of carbon in'the presence of a hydrogenation catalyst to produce hydrocarbons and oxygenated organic compounds. More particularly in this aspect the invention relates to the hydrogenation of carbon monoxide in the presence of an iron catalyst of a specific composition under conditions to produce a relatively high yield of oxygenated compounds. In another aspect this invention relates to 'the hydrogenation of carbon monoxide in the presence of an iron catalyst of a particular composition under conditions to produce a relatively high yield of hydrocarbons useful as motor fuel.

It has been known for some time that hydrogen and carbon monoxide may be made to react exothermically in the presence of catalysts under specific reaction conditions to form hydrocarbons and oxygenated compounds having more than one carbon atom per molecule. In general, the synthesis of these organic compounds by the hydrogenation of carbon monoxide is accomplished in the presence of a metal or an oxide of a metal chosen from group VIII of the periodic table as a catalyst, at pressures below about 500 pounds per square inch gage and at temperatures below about 750 F. for the production of hydrocarbons and at pressures between about 1,000 and about 10,000 pounds per square inch gage and at temperatures above 750 F. for the production ofoxygenated compounds. I I A v The synthesis feed gas or reaction mixture comprises a mixture of about one to two mols of hydrogen per mol of carbon monoxide and may be prepared by the catalytic conversion of natural gas, steam, and carbon dioxide.

Various methods have been practiced to effect the'reaction of hydrogen and carbon monoxide to produce organic compounds. Among these methods are those known as fixed-bed catalyst operations and fluid-bed catalyst operations. The fixed-bed operation comprises passing a reaction mixture of hydrogen and carbon monoxide through a stationary bed of catalyst in a reaction zone, and the fluid-bed operation comprises passing a reaction mixture through a finely-divided catalyst mass suspended in the reaction mixture in the reaction zone.

It is an object of this invention to provide a process for the synthesis of organic compounds having more than one carbon atom per molecule.

It is another object of this invention to provide a process for the production of oxygenated compounds in a relatively high yield by the reaction of carbon monoxide and hydrogen in the presence of a hydrogenation catalyst.

8 Claims. (01160 1495),

Another object of this invention is to provide a process for the production of hydrocarbons useful as a motor fuel in relatively high yield by the reaction of carbon monoxide and hydrogen in the presence of a hydrogenation catalyst.

Still another object of this invention is to provide a novel catalyst for the hydrogenation of carbon monoxide.

A further object of this invention is to provide a method for producing a hydrogenation catalyst useful for the hydrogenation of carbon monoxide.

It is still a further object of this invention to provide a particular novel catalyst adapted to the fluidized process for the hydrogenation of carbon monoxide to produce a particular organic compound.

Yet another object is to provide a process for the synthesis of organic acids. 1

Various other objects and advantages will become'apparent to those skilled in the art from the accompanyingdescription and disclosure.

According to a preferred embodiment of this invention,'I have found that a metal or metal oxide hydrogenation catalyst containing between about 0.1 per cent and about 2.5 per cent by weight of an oxide of potassium is very effective for the hydrogenation of an oxide of carbon to produce a high yield of organic compounds having more than one carbon atom per molecule. For maximum yields and selectivity, a metallic iron or iron oxide catalyst containing between about 0.2 and about 2.0 per cent by weight potassium oxide, K20, is preferred. A potassium oxide content above about 2.5 weight per cent results in excessive formation of wax on the catalyst, which decreases the activity and life of the catalyst; while a potassium oxide content below about 0.1 weight per cent results in substantially increased yields of carbon dioxide, methane, ethane, and other low molecular weight hydrocarbons.

It has'further been found according to this in vention that the amount of potassium oxide in the catalyst is critical with respect to the type of product produced. Thus, for. the production of oxygenated compounds, especially the relatively high molecular weight'alcohols and organic acids, the catalyst must contain at least about 0.8 weight per cent, and preferably between about 1.0 and about 1.5 weight per cent potassium oxide. When it is desired to produce relatively high molecular weight hydrocarbons accompanied by a minimum amount. of oxygenated compounds, it has been found that the catalyst must contain between about 0.8 per cent and I organic compounds.

about 1.5 per cent'KzO produces a much larger amount of oxygenated f action conditions, In fact, in some instances, as

V much as four or five times as much oxygenated z 7 'c'ompoun ds are produced by such a high alkali I catalyst as with a lower alkali catalyst. Of the oxygenated compounds produced; with the high alkali f'catalyst, the normal alcoholsfsuch as Compounds than a metallic iron catalyst of lower 1 potassium oxide content 'under comparable re l a "4 I Y s V or it may be merely on the surface of the hydrogenation catalyst uncombined therewith in any way. For example, a naturally occurring magnetite may be 'mix'edrwith an appropriate amount} of potassium g h d io'xide' or. potassium carbonate and the resulting mixture fused. The

:4, the ultimate catalyst in a fused condition with ethanol, propanol; butanolyand pentanol, along j with such organic acids as aceticypropionic, and butyric acids comprise the majorportion of they;

olefinic and are present in the product in. a relae tively larger-proportion than in the product of the low' alkali'xcatalystJ It is possible to operate I I H with the'high alkaliucatalyst at relatively higher temperatures than is possible.;with;;low;.alkali 3 catalysts. withoutexcessive formation, ofcoke' on 1 theocatalyst 1 V r r Qmcthemthenhand; itzhas'rbeen foundsthatgia lomalkaliiron catalyst containing between about Di per- .cent and abouta ofl per cent. potassium I oxidaproducesathamaximum yieldoi .hydrocar-; bons; 'Irr-the hydrogenation or carbon monoxide with a low alkali catalyst according to thisuin-v 1 ventioncth'eumaximumyieldiot hydrocarbons of high quality boiIingQ-Withinthe, gasoline. range 1 are obtained. ,o Furthermore, the -low.all;a1i iron 2 catalyst produces a hydrocarbon traction; useful as a ,diesel fuelof much higher quality than that v 'produ'cedwith; a highalkali catalyst. Relatively higherzspace;velo,cities= for; somewhat lower temperatures, maxvbeus d w th l iw, alkali 9812 IXSt QtHaHMWith the high, alkali catalyst for an qvui-ralentlc nversi n f; ar on nq da thou h p tas m ox deha been found tmb' the-much pre rr a vat n mp niwhe incorpora ed;w thrhydro ena ion: cataly 9. 13

fused mixture is then pulverized and reduced with hydrogen at a temperature between about 90035. anduabout. 1600" F. In this manner of preparationmhapotassium oxideris present in irony In another manner of preparation in which the, alkali is onthe'surfaceof the catalyst un-' combined with-the iron, naturally occurring magnetite is fused, pulverized, mixed with potassium carbonate, and the resulting mixture reduced. 7

The catalyst of thisinvention maybe employed in stationary or-fixed-bed condition, as wellia ithe fluid zed r. fillidi e onditio aho 7 even itz isgmucmpr ierr d; 0-; mblem; it fluidiz d; ondit o I K reatip one inyco tact:

upwardly n tam n nu nnr r ater amoun tass um i e Q ro uc n -the desired product:

hyd o en and-carbomoxi reac anisr er assed as, asesthro hthe ac ionrzcne d :1;- it Q sef ect -v t react-a 1 or. a 199N193 ti h arboap e eaq ant. Theq-gaseousimixtur is pass du wa d r t ro gh-the ma s, at lys a a, veloc t mbie t 2:! 1 uspend- 2 nt ai 1 he atal ma srth e s t eam? e ereblyc e velocity of the gas stream passing throughathe reac ion. Zone is s fii en l w to, m t n e catalyst massin-a dense,- fluidized pseudo-liquid condition Howeyenthe velocity may be sufliciently'high to entrain at least a substantial portion; of the finely-diyided catalyst in theagas strearn to form acontinuous catalyst phase which circulates with the fiowing gas stream, without departingQfromfthe scope of this 'inventionr In the former condition: the .catalyst mass may be saidto be suspended in thergas stream,but.,not

' entrained therein inthe sense thatthere is move.-

pr sin am talan r meta u q ida. o h r, ota

1 1 umicompou ds andpther QI emc- POWQ 15,; lkali; me al nds kaline tearth u' .h.-; s

arium ndl th um r abl o e n 1 ncar qrated with. h h roge t n c a yst 5. te-Ye qm tsi t r m1 1i;Q al fi t e e to I 7 2 enrcalcu a ed a z xi ean ba I Preferably such activating com 1 V 1 paunds of allrali metals and allgaline earthscon- 7 this pseudo-liquid condition ofoperationa small tain ioxygen in the form of the hydroxida, car.-

bonate, sulphate, silicate, phosphate, aluminate, chrgmateynitrate, andbor atei Potassiuimcarbonate nitrate, hydroxide, and chloride have shown-yer good results, particularly whenthese, V compounds were incorporated withv a hydrogena-V' tion-catalystcomprising iron in'quantities greater than about 038 weightper cent lflcalcul'ated as .highryiel ds jof; oxygenated:organielcomg 5 r poundswere produced. Mixtures'of. these com 1 pounds may be vused as theactivating material without, departing from, the scope of this invenl tion andI when'mixtures'. are; used the alkali content calculated as V the. oxide is consideredwas C eitheruthe total quantity offlcompoundsg oruthe qtani t k an? e m oun -The activating compound, such ment of the catalyst mass as suchin the direction of flowoi' the gas stream.. When operating with the catalyst in the pseudo-liquid condition it is preferred to maintain the upward velocity of the [gas stream suificiently high .to maintain f the fluidizedrcatalystr-mass in 'a highly turbulent condition in whichjthe catalyst particlescircw.

late'at a high rate intheipseudo-liquid mass. In

proportion of catalyst in the fluidized massmay become entrained; in the gas streamv emerging 'fr omgthe uppersurface of. the fluidized mass l h h z a a yst s ntrain d: s ni d away fromjhemass I Inthe present, process .it'ispreierred toemploy the-hydrogen .and. carbon; oxide inratios" such that there islani excess ofhydrogen. Therefore,

' the charginglrate in the presentprocessis. defined byreference to the ratelatwhich'the carbon oxide ischarged, in terms of standard cubic feet,.i n .-the

7 gas; term, ofthe carbon oxide, per hour per, pound H V ras'KzQ-mayf a be qrpqiatsdw hmabs rqseaa ncata s inzese iq;solution-one used.cend t cnithercwi oi thermetaljcatalystin'thedense pseudo-liquid 7 mass of catalyst. in the-reactionzonev Thefiuidized-process is preferably operatedl'at a minimum fipacaveloeity equivalent to charging rate; of about; 1 .(lstandard cubicioot of the carbon oxide reactant, :per. ;heur,-;pe1 pound of the metal. oatcubic foot of the carbon oxide is that quantity of a normally gaseous carbon oxide which would occupy one cubic foot at atmospheric pressure at 60 F., or an equivalent quantity of a normally liquid carbon oxide reactant. Generally, with fluidized dense phase operation and pressures between 1 50 and 300 pounds per square inch gage with the high alkali catalyst, a space velocity between about 4 and about 10 standard cubic feet of the carbon oxide reactant, per hour per pound of the iron catalyst is used. With the low alkali catalyst a space velocity between about 10 and about is used.

The catalyst employedin the present invention is a finely divided powder comprising a metal and/or metal oxide containing the appropriate amount of potassium oxide which is, or becomes in the reaction zone a catalyst for the reaction,

or a mixture of such metal or metal oxide and other catalytic materials or noncatalytic materials. While the catalyst powder consists essentially of such catalytic metal or metal oxide containing potassium oxide it may include also a minor amount of promoting ingredients, such as alumina, silica, titania, thoria, manganese oxide, magnesia, etc.

In this specification and claims the catalyst employed is described by reference to its chemical condition when first contacted with the reactants.

The catalyst is employed in a fine state of subdivision. Preferably, the powdered catalyst initially contains no more than a minor proportion by Weight of material whose particle size is greater than 25o microns. Preferably also, 1 the greater proportion of the catalyst mass comprises material whose particle size is smaller than 100 microns, including at least 25 weight per cent of the material in particle sizes smaller than 40 microns. A highly desirable powdered catalyst comprises at least 75 per cent by weight of material smaller than 150 microns in particle size, and at least 25 per cent by weight smaller than about 40 microns in particle size.

In the preferred form of the invention with the catalyst present in a pseudo-liquid condition, the powdered catalyst mass is maintained in a reactor substantially larger than the volume occupied by the catalyst mass in the fluidized condition. In this operation all but a minor proportion of the catalyst mass is contained in the dense fluidized pseudo-liquid mass, which may be designated as the dense phase of the catalyst. The dense phase of the catalyst occupies the lower part of the reactor while that part of the reactor above the dense phase is occupied by a mixture of gases and powdered catalyst in which the catalyst concentration is much lower, and of a different order of magnitude, than the concentration of the catalyst in the dense phase. This diffuse phase may be said to be a disengaging zone in which the solids lifted above the dense phase by the gas stream are disengaged therefrom and returned to the dense phase to the extent that such solids are present in the diffuse phase in excess of the carrying capacity of the gas stream at the superficial velocity of the gas stream. The latter is the velocity at which the gas stream would flow through the reactor in the absence of catalyst. In the dense phase the concentration of the catalyst in the gas stream varies from a maximum near the gas inlet to a minimum in the upper part of this phase. Likewise the concentration of catalyst in the diffuse phase varies from a maximum near the 6. upper surface of the dense phase to a minimum in the upper part of the reactor. Between the dense phase of high average concentration and the diffuse phase of low average concentration there is a relatively narrow zone in which the concentration of solids in the gas stream changes in a short space from the high concentration of the dense phase to the low concentration of the diffuse phase. This zone has the appearance of an interface between two visually distinct phases.

This operation ordinarily involves employment of catalyst powders and gas velocities such that a relatively small portion of the dense fluidized catalyst mass is carriedaway by entrainment,

and it is necessary, therefore, to provide means.

in the reactor for separating such entrained catalyst and returning it to the dense phase, or to provide means externally of the gas reactor to separate entrained catalyst from the gas stream and return it to the reactor, orotherwise to recover catalyst from the product gas stream...

When catalyst is permitted to pass out of the reactor by entrainment in the gas stream in either the pseudo-liquid operation or the continuous phase operation, it is necessary to return such catalyst to the reactor, or replace it with fresh or revivified catalyst, in order to maintain the desired volume of fluidized catalyst in the reaction zone.

The pseudo-liquid operation in which the finely powdered catalyst is employed in a form consisting of the metallic iron catalyst and containing at most minor proportions of promoting agents, other than potassiumoxide, provides veryv high catalyst concentrations inthe reaction zone. The employment of the finely, powdered metal catalyst in a fluidized bed with eflicient cooling means also is a factor in permitting the use of high catalyst concentrations, since it facili tates the removal of heat from the'relatively concentrated reaction zone. The pseudo-liquid operation, employing the finely divided metal catalyst, results in initial catalyst concentrations of at least 30 pounds per cubic foot of the fluidized dense catalyst phase, while the preferred gas velocities result in initial concentrations of 40 to 120, or more, pounds per cubic foot 01' dense phase. 'It. will be understood that these figures refer to the initial average concentration in the dense phase. The accumulation of reaction products on the catalyst particles as the operation proceeds reduces the catalyst density and increases the bulk of the dense fluidized mass.

With an iron catalyst containing an oxide of potassium, temperatures in the range of about 350 to about 750 F. are employed. Usually about 30 F. to about 50 F. higher temperatures are necessary with the high alkali catalyst than with the low alkali catalyst. With. the iron catalyst. pressures between atmospheric pressure and the maximum pressure at which condensation is avoided may be employed. It is desirable, however, to employ pressures of at least 50 p. s. i. and preferably about to about 500 p. s. i.

In this specification, pressures are expressed as pounds per square inch gage and gas volumes as cubic feet measured at 60 F. and atmospheric pressure.

The linear velocity of the gas stream passing upwardly through the dense phase is conveniently expressed in terms of the superficial velocity, which is the linear velocity the charge gas stream would assume if passed through the reactor in the absence of catalyst. This superficial velocity takes into account the shrinkage r comiented gas'g hafi V the productilliquid Azigaseeontainingtexcesaliye "dazogemis proces se sundereconditionsaefiiectivmto lrea'ctj-allpor: a portion; ofgthezcarbom monoxide;

i and aaportionlofothe productomixtu're;aftera'rev jm'omal bfidzheivgreater part of the liquidaproduct' t n is recycled: in; volumetrict ratios-,l to thefreshr feed 7 gasg'oflofill to ;I#:1.i- Sinceii-in-one-emhodiment 1' of thieiinvention; a relatively. large. amount I of V 3 oxygenated 'compound's are produced; a portion r "of the oxyg' enated organic'compounds comprising Ethe -relatively low boiling compounds,- such -as the k'etones and aldehygies; are separated andrecycled' to the hydrogenation reaction 'to-increase {the yield: of 'oxy'genated -grganio compounds of j relativelyihighboiling point; A 'similariefi'ect on i the production-of oxygenated organiccomp'ounde is M's'odc'complish'ed by reeyeling unsaturated compounds; siuchgasl-eolefine which have; been Separa-teclfrom the -efliuent or 'the hydrogenation reaction Unsaturated fand oxygenated {come 7 1 pounds from sources other than the processitself may: be:- introdu'ced "into theireactiom withoutf'de V l parting-from itheiscopeaofirthis invention; j

' 7 Fiuid operationsia Zaturedevel's which; aretrelativel'ychighs.as comf- 7 pared toj 'ithoseawhich woman-be: permissiblezain fixect catalyst bed; :operatiohs :u'nder: comparable mil/91111116 caused bygthemeaetion-sand:is; prefers-r ably ins-the. ranger ofzfromfllil 110x10 fGQtjIJBI'LSEG-e; i-ond; lystltphasezimwhichfthef catalyst; -is.ientrainediim the: flowing gaseous mixture, velocities as highias '40Ieettper'second-may-bensedia a r 1 The:- rea'ctants'i are :passedinto; andsthrough the: reaction; zoneat a space 'velocitmequivalent to lat leastihfistandard cubic feet of the;carb0m i oxide; pemhour per pound-e of metal .cata'lyst the dense: catalyst phase; In ztheihydrogenation I cfefcarbonz monoxide with 1the-.ir.on'-. catalyst :it' is;- preferred ito: operate. at a space; velocity equivaa 7 a f lent 11:01; at ieastjzmstandard a-zcu-bi'c feet of: carbon 'monoxideiper'hour.:peripound' of: iron;- catalystsin fthe dense.catalyst1phase: The charging-rate is.

V j defined: by; reference: to; the scarbonz monoxide re,-..

mutant;:sihce-ztheratio of. :the: hydrogen reactant, Q 1*toiethetcarbonimonoxideireactant inathe charge gas may airyiwithiniwide-lim-its; This ratio: of hydrogen ofi about. I iottenia high. tie-10141. Atxthelzliratio. the preferred;-icharging 7 rate of; hydrogen and carbon 1 mnnoxideiwould," therefore,:beat least. 14.0 stand-i ardg-iufiit; feet :iper homr per -pound bf irom'cata-e 131st inwthedense catalyst phasw At; :a 2:1: ratio thi'si prefenred' rate: wouldsbe 610 standard. "cubic ;feet o fihydrogen and carbon monoxide:

whenzzoperatin iswith:acontinuous catae carbon monoxide :ijsiusuallyzinzexoess :11 i an zprefe'rably at least I :1 and V The wolumeofi reactants, per: hour) per volume ofiiciens eepseudo-liquiiii catalyst phase depends n 'i uponl he chargeirate-andlaloiupon; theconceni trati'omoficatalystin' thedensetphase; the latter U being; afieoted rby theecondition of the catalyst and thegga velocityg Atthe preferred; gas veloci- V 'itiesementionediabove for the pseudo-liqui'd opera rtionjrandi wherr empIoyin'g: -an iron c'a'talyst; the minimum-flsp'ace velocity -'=ma h'edefined I as: 2 cubicteet ofe'caiibon monox-ide per: hour; per 1;nouridnfiromoatalyst? U V According to; a' prefer-red modification of: 7 this intentionia' -freshieed gas havinglam CO ratio hig'her than-the ratiol in which; thesexcomp'ounds jam omiertectato other ,c ompound's isaemployed ratio of ihydrogeni to; carbonemonoxide' argeto theireactortis increased to the guireisbyi recyclin'gta;.portiozr:.ofi theoun- -remoizaii ofi parteor al lzof;

: carried out: at temper openati ngmonditionsx, hiS'JQ H i S fnonrthes-e ie cei'lenhheatr transfer --canacityof; thefiuidiz fi theeffecti of eXcesshyciro en; in-;m'nimizingc neboln; formation. It is, pr rred-;: o v. oper te; at Whatev r temperature 1 ve .,:in; th ran e-0f. 3 05: 7 to. 1 50? Ft i z:nec.es. ary.toge i t hi h 094 har e-containing. more-hydrogen; the :carhen monoxide); pace. velo it s. equivalent o. at least 2 ,standa1:da; ubi. fee f ca bQmmQnQxide perghour' perr peundof iron;. oat alyst-in the-dense phase. I a

invent onw des 1ibed funtheniby refe e ceito thezac em anyin dra nawhich is; iazivievv n? el vation; partly sec io ni; a reactq v mplo e ri carr-yingeout' the r ent invention y' a; pseud r qu duop ratient and: by refer ce t espe fic xamplesxo zepenat ons m: od -me the, 1 mf ent inv ntion: an l a ned :out

ine apparatueexemplified; by the drawing. 7

r V flei mt n -gtect ieerm ne; reactor 1 on of n' thofiex-tra heavy zeinehzs eelp pezw. e sabput 2 0 nch en-3:, enema-inside a r. d tout-z e di m ter -1 i' n and" Q=: n. ies

' respectively. Reactor l is connected y ical section 2' to an'inlet pipe e3 made e v -i a r hw steel p e h.a+ ine ,.an diameter- 0f ;0.55-=inch; Reactor 1- is 00 at the top, by means of'a conical section 4,

' -im ra a i e e having: ny:

diameter of 7.63 inches; Conical ;sectio & J ane conduit '5 constitute an; enlarged: extension; of reactor which -iaoi1 itates: ieengagement of fiwithrconduitsland-'8'; t v, sections; of extra heavy 3 -inch" steel pipe duits 'l anti8--( :ont ai;n{filters 9 yandl ll wh eh ate constpuctetieof -p'orous;- material; which able to the-ga s; and. vapor s emergin i t, reaction zone but impermeable-to-the catalyst particles carried by 1 enttainn ent; in the gas stream Fi-lters Sand I 8,are cylindrioaiin shape angln cloeed atv the; bottomgendee They are ltd-i mensioned inrelatiorntoonduits- 'l and; 8 to p fioticieaasubstantialgnnulel space between he filter and the inner wall .:of the enclosing; duitgtiortthe passage 0f); ases andivapor and entrained f catalyst Vupward1y about the outell' surface-of: the filter; The upper ende; of; filters 7 5v and vH1 are mountesigin closure means; I I anq mustzpass through eithen-filten; 9 01% fi-lte T eYemeni-Ja k t x .e ends; o l h i-fiiinch pipe nwuit b em nner, as shown, v 7 Accessto the interior of jacket I 55s prov edby; a o eni e 5, the hem; through a- 2 -inch steel nip fiacketiltsie danted ar-conta n -hodyz e quid iemneratuxescon nebnur g e i wakes w ter; OW herm., The

- vap szwh ch' zatezevolivdr by. he heater; reaction niasewfv finely: divid irony. or :iron oxi e Midi V 1': j sion fs. carbon: mo ox d 7 when; treatin i a l as catalyst from thega s strearriatteripassage of 7 111T 'e e r b t es ciev mrs 9 are withdrawn at [6, condensed, and returned to the body of temperature control fluid in jacket I 5. The condensate returned to jacket [5 may be introduced through line [6, or directly at a low point, adjacent pipe 3, by an inlet means not shown. The temperature control fluid in jacket [5 is maintained under a pressure at which the liquid boils at the temperature desired in jacket I5. Heating coils, not shown, are provided in connection with jacket l5 to maintain the temperature control fluid therein at any desired temperature when it is desired to heat the contents of reactor I.

In order to show all the essential parts of the reactor and associated catalyst separation means on a single sheet, a large proportion of the apparatus has been eliminated by the breaks at I! and I 8. For a clear understanding of the relative proportions of the apparatus, reference may be had to the over-all length of the apparatus, from the bottom of jacket I5 to exit pipes 13 and I 4, which isabout 310 inches. In each of breaks I! and IS the portion of the apparatus eliminated is identical with that portion shown immediately above and below each break.

In pseudo-liquid operations carried out in this apparatus the catalyst recovery means, comprising filters 9 and H], are effective to separate substantially completely entrained catalyst from the outgoing stream of gases and vapors. The disengagementof solids from the gas stream is promoted by the lowered velocity of the gas stream in conduit 5 and remaining solids are separated on the outer surfaces of filters 9 and Ill. The latter are employed alternatively during the operation so that the stream of gases and vapors and entrained solids passes from conduit 5 through either the left or right branches of manifold 5 into conduit 1 or conduit 8. During the alternate periods the filter which is not in use is subjected to a back pressure of gas which is introduced at a rate sufficient to dislodge catalyst which has accumulated n the outer surface of the filter during the active period. Such blowback gas and dislodged catalyst flows downwardly in the conduit enclosin the filter and into manifold 6, in which the blow-back gas is combined with the reaction mixture flowing upwardly from conduit 5. The greater part of the catalyst thus dislodged settles downwardly into the reactor and is thus returned for further use.

The amount of catalyst charged to the reactor initially is regulated, with reference to any preliminary treatment of the catalyst in the reactor and the gas velocity to be employed, whereby the upper level of the dense phase is substantially lower' than the top of reactor l. During the operation the accumulation of deposited reaction products on the catalyst particles may cause an expansion of the dense phase and a rise in the height of the dense phase.

, In the operation of the apparatus of the drawing the desired quantity of powdered catalyst is introduced directly into the reactor through a suitable connection, not shown, in conduit 5. After any desired preliminary activation treatment-the temperature of the fluid in jacket I is adjusted, by the heating means mentioned above and by the pressure control means, to the temperature desired in jacket I5 during the reaction.

After the catalyst mass has reached the reaction temperature the introduction of the reaction mixture through pipe 3 is initiated. During the reaction the liquid in jacket I5 is maintained at the desired temperature by controlling its pressure. The reaction mixture may be preheated approximately to the reaction temperature prior to its introduction through pipe 3, or the reactants may be heated to the reaction temperature through the passage thereof through that portion of pipe 3 which is enclosed by jacket [5 and by contact With the hot catalyst. In most of the operations described hereinafter it was preferred to preheat the reaction mixture to temperatures of at least 350 F.

Pipe 3 is dimensioned with respect to reactor I and the desired superficial velocity whereby the velocity of the gases passing through pipe 3 is sufficiently high to prevent the passage of solids downwardly into pipe 3 against the incoming gas stream. An orifice plate, not shown, i provided in pipe 3 to prevent solids from passing downwardly out of the reactor when the gas stream is not being introduced into pipe 3.,

In this apparatus operating runs were made to test the efiicacy of the catalyst of this invention in the treatment of a gas charge containing hydrogen and carbon monoxide to convert these reactants to hydrocarbons and oxygenated compounds. In each operating run the alkali content of the catalyst was varied to test the effect of various combinations of catalyst compositions. The results of each operating run are represented by the results observed during a stabilized period of operation undera given combination of operating conditions. The conditions of operation and the results obtained in these operating runs are described below in the following example and tables.

EXAMPLE The catalysts for use in these operations were prepared from an ammonia synthesis catalyst which had been prepared by fusion of alumina and potassium oxide in molten iron oxide to produce a mixture of iron oxide, alumina, and potassium oxide. This material consisted principally of iron oxide and contained about 2.9 per cent alumina, about 3.4 per cent potassium oxide, and lesser amounts of titania and silica. To prepare this material for use in this improved process it was first ground to a 6 to 20 mesh size and then subjected to leaching with water to remove the desired amount of potassium oxide. This treatment reduced the potassium oxide content from about 3.4 per cent to'about 0.3, about 0.6, and about 1.4 per cent for three separate catalysts based on Fe. The leached material was then dried at 210 and reduced in a stream of hydrogen.

In the reduction treatment a heated stream of hydrogen was passed through the granular mass of iron oxide, treated to remove water formed by the reduction reaction, and then recirculated. The temperature was raised gradually and the reduction reaction was initiated at about 600 to 800 F. The temperature of the catalyst mass was then raised to about 1215 F. in two hours while continuing the flow of the hydrogen stream. During the next 4 hours the temperature was raised to approximately 1285 F., during which time the reduction was substantially completed, as evidenced by the practical cessation of water formation. The reduction is usually carried out at a temperature between about 1200 F. and about 1400" F.

Each of the reduced catalysts was ground in an atmosphere of carbon dioxide, first in ahand grinder and ,then in a ball mill, to produce a powder; s nailer-rtha r ieb: neuro and thawin 1 f -1RPI %Q :Y BB

- ammie gfollew-in wscreen an Rcllw traet on f :t econdjensed oil witheth ienee sa ol and bya a er r-z-serubhie 1 31 58085, action. .ilfhe grecoyery of oxygenated arsenic products from the-synthesis effluent isdiscusaegiy nwQn! ti re reached the,hydrogenistreamywas re lilacedijhy. astream oiesynthesi -i-gasuconsisting essentially ,ofhydrogen! and carbon monoxide in line desired ratio. ,Thesynthesis gasiwaspassed arjdly through reactor 1., at the ratesshoyvnJ-in flowing tables. At the1same timetthe out o et, ressureon the rea tor wasQgradually pounds and. 2150, pounds respec:

eifiuent was removed from. reactor 4. amen;

' reacted reactants-i andfpfo o s ;of the proc '7 .w renseparated therefrom. The. reaction prodil ts w re recovered ion the most part bywccoling' j'th'e reaction. m xture j to: room t temperature tor lower to obtain a condensate and by passing the .nncondensed gases throughan. absorber such? as fraction contained substantial amounts .of. may genated compounds, ,The absorbed products were recovered by. steam idistillation whiehyielded a light" naphtha "fraction, condensed water], and a ga seo us fr action. The WELtBl" contained additionaloxygenated compounds. The gaseous fraction w salmost ntirely hydroearhonsshavr .ing three to five carbon atoms, perwmolecule. .The

yie1d ,of the various fractionszwas jdetermined bylmeasurerrient of'the condensed product andby 7 absorption and combustion analysisofthe.gas

jfmm the condenser, Qxygenated communes we e-r everesiin most instance rom hepmdv r *uets hydi'stillation of th water prodn t,iby.,.ex-

.c y 7 .75 :siderab-ly more detail: in co-pezi'cli-ng -applications, 2' ".liolleroea us' s r f um er 709 7-1;a -'I09,872 filediN vem- ,c V i .:ber- 14,;l-94'6, now-=-Patent :Nes; 2,4'7fi';-'7a2-=and rmihcelm Q-rermm 'zjeihllwrespe v y; 30f whi h l'ti am a co- V n l 1', e. i i -v inventor. It is believed, therefore, that'i-t is un- I .10 -necessa;ry-to;1disc1 ss the recoyery o-f the-oxy en g altediproducts. -:in -detail ;in this application; since 7 r 'hetmence-maybemade to the aforesaidwdwend- 5 ing applications if necessary. I The tfollowing table shows the-:Qperatih eon- V H ;,ditions' andvresulting yields and selectiw iSiC n. na y Lya rions ;typi-ca1'runs -;for an iron catalyst-halvin l 1 y -Q-3 "Q- n 1.4-percentaKzO contentrrespec-i S. S t andar l S.ieye j PonG t tively. The -fivefir-unsillustratedwere selected V as representativecf the waniousrimsjmade in de- Tr gige. Q (terrain-111g thecharacteristicsof -the catalyst;

iiII'ABLE II V Comparisonofi .m'ul.v low. alkali, caytdlglstsa '25 yields..andi selectivitzj H ;Between.:;a*boutiii-$000 .andzaosooerams2hr hb i rr m i I M 1- ;cata.iystiithns prepared 'weretcharged into reactor g 1 r r 1 1 -lv'sthmt1ghaan: inleteinotsishown vl-intsection fi; g gg m v I V V, .surep.s.,1 .250 6250 .250 Invitin ::thls-roperationrzthev-catalystewas mam- Temperammpn .3 gm ainedtinzthelatmosphere of carbon-:dioxide and g g; ,;a;- sma1l;tream;of. 1-;or2 cubic feettoi icai' bonadi- :fixidexperihour was passedlupwardly through res actor-jjcogpreventpackingzofthe-catalyst; l miter 9 I t the catalyst was charged to reactor I, the carbon dioxide stream was replaced with a stream of 7- j hydrogen whichwae-pass d p a ly throu reactor. I. at the. rate of 15120 zowcubic ieetper 1 5.5 hour; v.Tlle. freactorewasu thensheated; externally y .whil ihydmgenrwaspassednpwardlythr ugh e r V reactoratthis rate @Wheh the desire tempera- 555 pounds 1 Based on total 1 fI-he-nesmtsohtained withthe. warious-catalysts containing edifierentJ-potasium oxidecontents ginfidicaiied thatthe' catalysts -containingethe smaller amounts of ..alka1i-;were most-active -in the, .con-

version' .of carbonimonoxidef relative-ac tivity is 'seen in the foregoing table-in:the fact that the high alkali catalyst required a-:higher temperatureand alower space velocityto obtain approximatelylsthe same amount of CO conver sion .as thelower alkali catalyst. V

comparison of the yields and of ithe selectivity of the three catalysts is also foundvin the foregoing table. .N.o allowance has; beenemade' forhpossible'losses th va ou recoyery ystems. Examination of Table II indicatesthat, thevcata ducedlmore. than four times as .much; "oxy en 7 ated compounds asdid the, lower .alkaliicatalyst.

7.5 gene ally, thehiigh alkali catalyst hadrasi gliily yst. containing a higher amount of. ,alkali r olower'hydrocarbon yield than the loweralkali catalyst. At comparative space velocities, the high alkali (1.4 percent K20) catalyst produced slightly more low boiling hydrocarbons than did the 0.6 per cent K20 catalyst, but the low boiling hydrocarbons were formed at the expense of a decrease in yield of 400 F. end point gasoline.

The oxygenated compounds with the low alkali catalyst were predominantly alcohols and are produced concurrently with the hydrocarbons and are considered very valuable products. With the high alkali catalyst, the acid product was almost equal to the alcohol product. The catalyst containing the 1.4 per cent K20 produced a much larger amount of oxygenated organiccompounds than did the other catalyst. For example, the operation shown with the 1.4 K20 catalyst resulted in 47 cc./m. of oxygenated compounds as compared with-the 0.6 percent K20 catalyst and the 0.3 .per cent KzOcatalyst which produced 12 and 8 cc./m. respectively. The high alkali catalyst also produced somewhat larger proportions of total liquid products than did the lower alkali catalyst, as is noted in Table II. The relative CO distribution for the various catalysts shown in Table 11 under Selectivity clearly indicates the'greater selectivity exhibited by the 1.4 per cent K20 catalyst where approximately 55 per cent of the CO was'converted to liquid hydrocarbons and chemicals, as compared with 44.5-53.7 per cent for the other catalysts. As previously mentioned the yields of oxygenated compounds were much greater with the high alkali catalyst than with the low alkali catalyst. I

Table III shows a comparison of the distribution of the oxygenated compounds for the 1.4 per cent K20 catalyst and the 0.6 per cent K20 for operating conditions given in Table II. The normal straight chain primary alcohols are substantially the only type of alcohols produced with either catalyst. The most striking difference between the oxygenated compounds from the two catalysts was in the acid content which was almost negligible with the 0.6 per cent K20 catalyst and was as high as about 34 per cent of the total oxygenated chemicals with the 1.4 per cent K20 catalyst. It is also noted that there was a shift toward a substantially larger production of high alcohols with the 1.4 per cent K20 catalyst.

TABLE III Comparison of high and low alkali catalystyoxygenated compound distribution Alkali Content-K O percent by weight 1.4 0.6

Distribution of Oxygenated CompoundsVol. Percent:

Acetaldehydc and Propionaldehyde 2. 2 Acetone. 0. 9 8. 6 yl Ethyl Kctone 0.5 5. 7 Miscellaneous Aldehydes and K nos in O 9. l M Alc hol 1.2 25. 8 46. 9 5. 2 26.8 4. 8. 3 1. 7 l. 4 2.0 1.4 Hcptyl+Higber Alcohol: 5. 1 0. 9

AceticAcid...... as Propionic Acid t. 6 Butyricl-Highor Acids 19. l

Total Acid 33.

Esters s. 8'

1 Negligible.

, carbons fromthe highalkali catalyst included more olefins than those from the low'alkali catalyst. The difference is Lparticularly,noticeable in the low boiling hydrocarbons, i. e., from C2 to C4 hydrocarbons.- The light gasoline recovered from the charcoal absorber-had approximately the same olefinic content for eachcatalyst but the heavy oil and waxfor the. operation with the high alkali catalyst showed much less unsaturation than did the heavy oil and wax {for the low alkali catalyst. This large difference in the olefinic condition of the heavy oil and wax was probably caused by the presence of non-hydrocarbons, such as alcohols and acids-and therefore the actual values based on the hydrocarbon alone would probably show muchcloser agreement; for example, the heavy oil and wax from the 'high alkali catalyst contained to per cent oxygenated compounds and on the other hand the same material from the low alkali catalyst contained about 5 or 6 per cent oxygenated compounds.

TABLE IV Comparison of high and low alkali catalystsolefin content of hydrocarbon fractions 1 Based on total fresh feed (CO-+112) Since in commercial processes the C3 and the C4 olefins could be polymerized to form polymer gasoline, the distribution of the liquid hydrocarbons after the formation of 10 lb. R. V. P. gaso- ,line with the incorporation of the polymer are summarized in Table V. The gasoline fraction for the 1.4 per cent K20 catalyst was an appreciably larger portion of the total liquid hydrocarbons because of the large amount of polymers obtained from unsaturated Cs to C4 fraction. It should be noted that the high alkali catalyst produced insuflicient C4 hydrocarbons to make 10 lb. R. V'. P. gasoline after polymerization while on the other hand the low alkali catalyst produced an excess amount of light hydrocarbons amply sufficient for the'production of 10 lb. R. V. P. gasoline.

The 400 F. end point gasoline inspections are also summarized in Table V. For comparative space velocity with the 1.4, 0.6, and 0.3 per cent K20 catalyst the yields of gasoline including polymers was lowest for the 0.3 catalyst and highest for the 0.6 catalyst. The 400 F. end point gasoline yield (03+) with the added polymer was about 20 cc./m. less from the high alkali catalyst than from the lower alkali catalyst. The large increase in gasoline yield when the catalytic polymer is included was caused by both the large yield of olefinic hydrocarbons and the large yield of relatively low boiling hydrocarbons, such as C3 and C4 hydrocarbons. This was particularly the case with the gasoline produced from The product water from the high alkali catalyst operation using a 1.4 per cent K20 catalyst contains a large concentration of organic oxygenated chemicals, such as acids, alcohols, ketones, aldehydes, and esters. Additional water soluble chemicals were dissolved in the heavy oil and could be removed by water washing. The oil also contained water insoluble material. The separation, analysis, and identification of the oxygenated compounds in the water was accomplished primarily by precise fractionation, sometimes followed by preparation and examination of derivatives. To simplify the separation and recovery problem, the acids were first neutralized with caustic. Below are listed some of the compounds and azeotropes which were identified from the distillation curve by their boiling points and by analogy with previous distillations.

Acetaldehyde Acetone-methanol Methanol Ethanol-ethyl acetate Ethanol-methyl ethyl ketone Ethanol-water Propanol-water ButanoL-water The above compounds and azeotropes collectively accounted for about 16 per cent of the high alkali catalyst water product of which about 7.5 per cent or 47 per cent of the overhead was ethyl alcohol-water. Less in quantity was the propanol-water alcohol amounting to about 2 per cent or 16 per cent of the overhead.

An analysis and distribution of the oxygenated Volume per cent. Alcohols:

Methanol 1.2 Ethanol 25.8 Propanol 5.2 Butanol 4.0 Pentanol 1.7 Hexanol and higher 7.1 Acids:

Acetic 9.8

Propionic 4.6 Butyric -1 4.5 Valeric 2.6 Caproic and higher 12.0

The average distribution of total oxygenated compounds was about 60 .per cent in the product water and gas and about per cent in the oil. Ethanol was the most abundant of the non-acids produced and of the acids the lighter acids were most predominant, i. e., acetic, propionic, and butyric.

In the operation using the high alkali catalyst containing 1.4 per cent K20 several catalyst samples were withdrawn from the reactor during operations to determine changes in analysis of the catalyst as the catalyst age increased. Oil and wax deposits were removed from the catalyst by xylene extraction. A sample of the extracted catalyst was next burned in a combustion tube in an atmosphere of oxygen and the resulting CO2 measured to determine carbon. Another oil and Wax free sample was used for chemical determination of iron. Data obtained from these analytical procedures and size analyses are shown in Table VIII.

TABLE VIII Powdered iron catalyst-1.4% K2O-anaZyses Re- Dis- Run Fresh charge 1 2 3 4 5 6 charge Catalyst Age-Hours .1 0 372 545 611 721 761 804 882 931 Operating Conditions:

Temperature F 580 590 586 590 610 633 628 630 Pressure-p. s. i 8-250 250 250 400 250 250 250 250 H CO 2.5 2.3 2.1 2.5 2.3 1.9 2.1 2.8

14.1 9. 8 26. 0 27.3 12. 6 101 1 6. 9 7. 6 17.1 18.9 15. 8 16. 3 22. 0 23. 4 23. 6 24. 0 50. 9 40. 7 43. 3 45. 0 55. 2 63. 8 58. 0 60.0 a 9.1 21.5 7.7 5.2 2.7 7.8 2.8 1.0 I ""633" III: III: III: III: III: III: III: Total Fe l 57. 9 57. 4 49. 3 49.1 57. 2 57. 9 60.1 60. 7 Lb. ./1001b. 6 173 174 203 204 175 167 161 165 Lb. C/100 1b. Fe. 0 29. 5 32. 32. 1 33. l 38. 39. 1 39. 3 39. 5

compounds produced with the 1.4 per cent K20 catalyst are shown in Table VII below.

' From the data in Table VIII it is evident that a high alkali catalyst could be operated at relatively high temperatures (630 F.) without excessive coke formation. A period of very small change in carbon formation was attained after about 400 hours and maintained for an additional 350 hours. With the low alkali catalyst containing 0.6 per cent K20, a similar steady state was reached after about 450 hours and maintained for about 200 hours. This steady state condition with the low alkali catalyst was about 23 lbs. catalyst/ lbs. of iron while with the high alkali catalyst it was about 33 lbs. cata-' lyst/ 100 lbs. of iron. An estimate of the relative volumes of original and approximately steady state catalyst indicated that the latter material would occupy nearly four times the original volume.

isdeemedunnecessary. -It should be notedyhowa fAlthough the 'rejdiiced rermgmous catalyst or this example 'has been consfideredfito have an t ltimateijd mp sit o m iicii r n d t 7 'Havingneseribea my invention, I cla' imz 'l'able 1:: is tabulated operating ferent alkali contents and 150 pounds per sguare catalystis much larger than the low alkali' c'ati alyst eyen'atdowpressures of aboutl 50 pounds. "The discussion of -Table-I-I;wi-l1-applyfin rngst resiiects-torthe-analysis-of the data in Table IX v conditions? an [yields for the various catalyst having difand consequently furtherrdiscussiongf Table IX eye i--;th 21 611 13 i T b el;.. u n a i Y the; d ta- T l .1,. and th d l i n nectiontherewith. The-analysis of the oxygenated compounds, the gasoline fractio'ns and vari- .ous other -fractions-as discussed in connection an hfi qngl ndz ressur e at nswas un to be quite similar with the 150 pound operation V as S hQWn in Table 12; below: TABLE 1x 1 Cubicc'ntinie'ters pi cnbicmetr'bf total fresh'feed. Nor ecycle. V

the actualf composition of tne catalyst may contain' considerable iai'nbfunts 'of uni'duced oxides 7 of iron. For convenienceland clarity-the K20 'contentfiisicalculated onthe basis that all the Fe in the catalyst is present agrnetallic ironm'so altholigh the -'-potas'siu-rn-content of 'the-catpresent-in {fither forms the &0.

- va'iriousf'minor-modifications tneapii'aratus 1. a procss for hydrogenatmg garbo monhich comprises "continuously flowinga re comprising hydrogen and "car'- between about 0.8 and'about 2.0 weight per nt st ontaining-a thecata-l wally *ajsub stanti'al quantity of oxygenated 1 v compounds having more than "one carbon atom ide' per hour per pound or metal c atalyst'm "the "dense, fluidi'ieidhia'ss or Catalyst maintaining a V ractiontemperature between aboup ssoegnand 1 about 750? F. and ?a reaction pressure tween about 50and about 500 poun'dsper'square inch gage, withdrawing an eiiiue'nt from-sai eaction zone aftr p'assage of said gasfeous ihixture through the dense catmsvmass, and ree verinfg permolecule from said effluent as products of the process. a

2. A'process for producingoxygenated compounds by the hydrogenation {of carbon monox ide with a fiuidizedcatalyst which'comprises continuously flowinga gaseous mixture comprising hydrogen and carbon monoxide in 'a'feed ratio of hydrogen to carbon monoxide between about 0.7:1 and about :1 upwardly in a reaction zone in the presenceof a finely'diyide'd iron catalyst containing metallic'iron as the essential catalytieally a'ctiye ingredient and between about 0.8 and about 2.0 weightper cent potassium oxide, flowing said. gaseous mixt'ure' upwardly through said reactiomzcne-at'ayelocity su'ch that finely di' 'lided'cataly'st is fiuidized,'maintaining in said "reaction fz'o'ne a tem eratur between about 580 and about 750 F. and a pressure between about 50 and ab'out'500'p'oundsper square'inch gage,

f yKaopercent byweight "0;7 033 1:4

Operating Conditions: ,lours on condition; 235

, Pressure p si-i 1 15,0

-Temperature F I 5 583 Space. \lelocity 415 CF./ hr./lb-./Fe 21-6 39.9 18.9 Recycle Ratio-Re/fl 1. 8 1. 17 H,:GQgFie-sh Feed" 7 .0 ..-1.-,6 1. 6 I 0 -2.15 2.4 .8 -52ss 53.0 v. .1 89.7: 87.2 Yi

V 27 i 14 41 '61 45 20. 73 72 43 'i I 124: 121: Oxygenated Opds. 8 '5 32 Total liquid (hy'dr 132 153 -]Vater 79 85 75 1 Selectivity Per Gent: ,i V v 1 i 1 "C090 2..." 28.4 30.0 31.8

' "COQOXYgeITa "6.0' "1T6 1176 f OO')C;+O 13. 3 118. 4 13, 0 00-)0 -1- 34.6 28.9 29.4

withdrawing an efiiuent from saidreaction zone, 7

separating a substantial quantity of oxygenated compounds having more than one carbon atom per molecule from, said eiiluent as products of we process, and recycling a gaseous mixture comprising an unreacted reactant to said reaction zone ina recycleto freshfeed volumetric ratio ofabout 0.5:1 to about 10:1.

7 3. The. process according to claim 2 in which tial catalytically active ingredient, and between about 11) and about 1.5 weight per cent potas- V sium oxideto -suspendthe catalyst mass in said apparent to"- thosefskilld-m th ai-twithout degastritis mixture, "passin said gaseous fmixture,

through said mass at a velocity suffi'ciently low to maintain the mass irr a dense, fluidized pseudoliquid condition but'sufiiciently high to produce rapid circulation of the catalyst particles in the massran'd at a feed rate equivalent to atieast 1.0 standard cubic feet of carbon monoxide per hour per pound of iron catalyst-in 'the dense, fluidized mass of catalyst, charging-to the" process a fresh feed mixture comprising hydrogen and carbon m noxide n H roge t m bo mom 7 oxide ratio between about 0.7 {1; and about 10:1,

maintaining a temperature betvs'leen about; 580 7 F. and about 750 'F. and a pressure between about and about 300 pounds per squareinch gage in said'reaction zone, 'withdrawin a'lga'seous eflluent'from-saidreaction zonei fteri as sag of-saidgaseousmixturef thrriugh"saidfilense catalyst mass, treating the gaseous efiiuent to separate a substantial quantity of organic acids therefrom as products of the process, and recycling a mixture comprising unreacted hydrogen and carbon monoxide at a volumetric ratio of recycle to fresh feed of about 0.5:1 to about :1.

5. A process for hydrogenating carbon monoxide with a fluidized catalyst to produce a relatively high yield of oxygenated organic compounds having more than one carbon atom per molecule which comprises contacting a gaseous mixture comprising hydrogen and carbon monoxide with an iron catalyst containing metallic iron as the essential catalytically active ingrediout thereof and more than about 1.0 and less than about 2.0 weight per cent of potassium oxide at a reaction temperature between about 580 and about 630 F. and a pressure between about 50 and about 500 pounds per square inch gage under conditions such that water, hydrocarbons and oxygenated organic compounds having more than one carbon atom per molecule are produced, suspending said iron catalyst in a fluidized condition in said gaseous mixture, withdrawing from the reaction a gaseous effluent containing prod ucts of the reaction, cooling and densing said effluent to form a hydrocarbon phase and a liquid aqueous phase, and treating both the hydrocarbon phase and the aqueous phase to separate a substantial quantity of oxygenated organic compounds having more than one carbon atom per molecule therefrom as products of the process.

6. A process for hydrogenating carbon monoxide with a fluidized catalyst to produce a relatively high yield of oxygenated organic compounds having more than one carbon atom per molecule which comprises contacting a gaseous mixture comprising hydrogen and carbon monoxide with an iron catalyst containing metallic iron as the essential catalytically active ingredient thereof and more than about 1.0 and less than about 2.0 weight per cent of an alkali metal oxide at a reaction temperature between about 580 and about 630 F. and a pressure between about 50 and about 500 pounds per square inch gage such that water, hydrocarbons and oxygenated organic compounds having more than one carbon atom per molecule are produced, suspending said iron catalyst in a fluidized condition in said gaseous mixture, withdrawing from said reaction a gaseous effluent containing products of the reaction, cooling and condensing said reaction effluent to form a hydrocarbon phase and a liquid aqueous phase, and recovering a substantial quantity of oxygenated organic compounds having more than one carbon atom per molecule from said liquid aqueous phase as products of the process.

7. A process for hydrogenating carbon monoxide with a fluidized catalyst to produce a relatively high yield of organic acids which comprises contacting a gaseous mixture com-prising hydrogen and carbon monoxide with an iron catalyst containing metallic iron as the essential catalytically active ingredient thereof and between about 1 and about 1.5 weight per cent of potassium oxide at a temperature between about 590 and about 630 F. and a pressure between about and about 300 pounds per square inch gage such that acetic, propionic and butyric acids, water and hydrocarbons are produced, suspending said iron catalyst in a fluidized condition in said gaseous mixture, withdrawing a gaseous efiiuent containing the products of reaction, cooling and condensing said effluent to form a hydrocarbon phase and a liquid aqueous phase and thereafter recovering a substantial quantity of acetic, propionic and butyric acids as products of the process.

8. A process for hydrogenating carbon monoxide with a fluidized catalyst to produce a relatively high yield of oxygenated organic compounds having more than one carbon atom per molecule which comprises flowing a gaseous mixture comprising hydrogen and carbon monoxide through a reaction zone in the presence of a finely-divided iron catalyst containing metallic iron as the essential catalytically active ingredient and between about 0.8 and about 2.0 weight per cent of an alkali metal oxide at a velocity eifective to fluidize said finely-divided iron catalyst in the gaseous mixture in said reaction zone at a reaction temperature between about 580 F. and about 750 F. and at a pressure between about 50 and about 500 pounds per square inch gage to produce oxygenated organic compounds having more than one carbon atom per molecule, withdrawing an effluent from said reaction zone after contact of said gaseous mixture with said catalyst and recovering a substantial quantity of oxygenated organic compounds having more than one carbon atom per molecule from said efliuent as products of the process.

HENRY G. LlCGRATH.

REFERENCES CITED 4 The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,743,214 Herold et al Jan. 14, 1930 1,801,382 Wietzel et a1 Apr. 21, 1931 2,225,487 Roelen Dec. 17, 1940 2,248,099 Linckh et a1. July 8, 1941 2,276,693 Heath Mar. 17, 1942 2,360,787 Murphree et al Oct. 17, 1944 2,436,962 Gaucher Mar. 2, 1948 2,455,419 Johnson Dec. 7, 1948 ,474,84 enny et al July 5, 1949 OTHER REFERENCES Audibert et al., Industrial and Engineering Chemistry. vol. 21, No. 9, pages 880-885 (Sept. 1929). 

8. A PROCESS FOR HYDROGENATING CARBON MONOXIDE WITH A FLUIDIZED CATALYST TO PRODUCE A RELATIVELY HIGH YIELD OF OXYGENATED ORGANIC COMPOUNDS HAVING MORE THAN ONE CARBON ATOM PER MOLECULE WHICH COMPRISES FLOWING A GASEOUS MIXTURE COMPRISING HYDROGEN AND CARBON MONOXIDE THROUGH A REACTION ZONE IN THE PRESENCE OF A FINELY-DIVIDED IRON CATALYST CONTAINING METALLIC IRON AS THE ESSENTIAL CATALYTICALLY ACTIVE INGREDIENT AND BETWEEN ABOUT 0.8 AND ABOUT 2.0 WEIGHT PER CENT OF AN ALKALI METAL OXIDE AT A VELOCITY EFFECTIVE TO FLUIDIZE SAID FINELY-DIVIDED IRON CATALYST IN THE GASEOUS MIXTURE IN SAID REACTION ZONE AT A REACTION TEMPERATURE BETWEEN ABOUT 580* F. AND ABOUT 750* F. AND AT A PRESSURE BETWEEN ABOUT 50 AND ABOUT 500 POUNDS PER SQUARE INCH GAGE TO PRODUCE OXYGENATED ORGANIC COMPOUNDS HAVING MORE THAN ONE CARBON ATOM PER MOLECULE, WITHDRAWING AN EFFLUENT FROM SAID REACTION ZONE AFTER CONTACT OF SAID GASEOUS MIXTURE WITH SAID CATALYST AND RECOVERING A SUBSTANTIAL QUANTITY OF OXYGENATED ORGANIC COMPOUNDS HAVING MORE THAN ONE CARBON ATOM PER MOLECULE FROM SAID EFFLUENT AS PRODUCTS OF THE PROCESS. 